CN110552028A - preparation method of antibacterial nano-porous material - Google Patents

preparation method of antibacterial nano-porous material Download PDF

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Publication number
CN110552028A
CN110552028A CN201910921944.5A CN201910921944A CN110552028A CN 110552028 A CN110552028 A CN 110552028A CN 201910921944 A CN201910921944 A CN 201910921944A CN 110552028 A CN110552028 A CN 110552028A
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porous
porous titanium
nano
titanium alloy
antibacterial
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CN201910921944.5A
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CN110552028B (en
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李烨
王建忠
敖庆波
马军
吴琛
荆鹏
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Northwest Institute for Non Ferrous Metal Research
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Northwest Institute for Non Ferrous Metal Research
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/54—Treatment of refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment

Abstract

The invention discloses a preparation method of an antibacterial nano porous material, which comprises the following specific steps of firstly taking porous titanium or a porous titanium alloy as a cathode, taking graphite or a platinum sheet as an anode, taking a copper sulfate solution as an electrolyte for electrodeposition, depositing Cu 2+ in the electrolyte on the surface of the porous titanium or the porous titanium alloy, and then sequentially carrying out heat treatment and nitric acid leaching to obtain the nano porous material.

Description

Preparation method of antibacterial nano-porous material
Technical Field
The invention belongs to the technical field of medical inorganic antibacterial materials, and particularly relates to a preparation method of an antibacterial nano porous material.
Background
antibacterial materials are generally classified into two categories, namely, organic antibacterial agents and inorganic antibacterial agents. In recent years, with the rapid development of medical technology, various effective organic antibacterial materials have been developed. The main varieties of the organic antibacterial materials are quaternary ammonium salts, imidazoles, halogens, phenols and the like. Among them, the quaternary ammonium salt antibacterial material is favored because of its excellent characteristics of low toxicity, low price, broad-spectrum antibacterial property, etc., and is the most widely used organic antibacterial material at present. However, the safety and stability of the organic antibacterial material are always important obstacles for the popularization and application of the organic antibacterial material. At present, inorganic antibacterial materials mainly utilize the antibacterial capacity of metals such as silver, copper, zinc and the like. Firstly, metals (or ions thereof) such as silver, copper, zinc and the like are fixed on the surface of a base material by a certain preparation method to prepare the antibacterial agent, and then the antibacterial agent is prepared into a corresponding product, namely the material with antibacterial capability.
The nano antibacterial material is a novel inorganic antibacterial material which is gradually paid attention by extensive researchers in the early 90 s of the 20 th century internationally and is developed rapidly. The material has the functions of self-inhibiting and killing bacteria. At present, the problem that the nano antibacterial material cannot realize sterilization and the problem that the surface of the nano antibacterial material cannot realize a self-cleaning function in the antibacterial process exist.
disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing an antibacterial nano-porous material, aiming at the defects of the prior art. The method sequentially adopts electrodeposition and heat treatment to enable Cu to be attached and diffused into porous titanium or porous titanium alloy to form multi-element alloy, then nitric acid is adopted to carry out acid leaching to remove copper in the multi-element alloy and form nano holes, oxidation is carried out simultaneously, and thus a needle-shaped nano porous titanium oxide surface layer is formed on a porous titanium or porous titanium alloy matrix to obtain a nano porous material with uniformly distributed nano holes, the surface of the nano porous material is provided with the needle-shaped nano porous titanium oxide which can pierce the surface of bacteria and generate capillary suction, the antibacterial and bactericidal functions are realized, and the self-cleaning function is realized.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of an antibacterial nano-porous material is characterized by comprising the following steps:
taking porous titanium or a porous titanium alloy as a cathode, graphite or a platinum sheet as an anode, and copper sulfate solution with the mass concentration of 10% -30% as electrolyte, and performing electrodeposition to enable Cu 2+ in the electrolyte to be deposited on the surface of the porous titanium or the porous titanium alloy;
Secondly, placing the porous titanium or the porous titanium alloy with the surface deposited with Cu 2+ in the step one into an argon furnace for heat treatment, wherein the temperature of the heat treatment is 300-800 ℃, and the heat preservation time is 1-5 h;
And step three, placing the porous titanium or the porous titanium alloy with the Cu 2+ deposited on the surface, which is subjected to the heat treatment in the step two, into a nitric acid solution for acid leaching treatment to obtain the nano porous material, wherein the mass concentration of the nitric acid solution is 30-60%, and the temperature of the acid leaching treatment is 30-70 ℃.
The method comprises the steps of firstly depositing Cu 2+ on the surface of porous titanium or a porous titanium alloy by an electrodeposition method to enable the Cu to be uniformly distributed on the surface of a porous titanium or a porous titanium alloy matrix and to form tight combination, then carrying out heat treatment to enable the Cu attached to the surface of the matrix to rapidly enter the interior of matrix metal through atomic diffusion under the high-temperature condition to form a titanium-copper multi-alloy, then carrying out acid leaching treatment to remove the copper in the multi-alloy, forming nano-scale diffusion lines in the porous titanium or the porous titanium alloy matrix while the Cu is rapidly diffused into the matrix metal in the high-temperature heat treatment process, dissolving the copper in the multi-alloy in nitric acid after acid leaching treatment to leave nano-porous layers on the surface of the porous titanium or the porous titanium alloy matrix, forming the nano-porous layers on the surface of the porous titanium or the porous titanium alloy matrix due to the oxidizing inorganic acid, having an oxidizing effect on the porous titanium or the porous titanium alloy, forming a nano-porous titanium surface layer on the porous titanium or the porous titanium alloy matrix, obtaining a nano-porous material with uniformly distributed nano-porous titanium, having a needle-like inorganic acid oxidizing effect on the nano-needle-like titanium oxide, having a nano-needle-like function, and further having a nano-like bactericidal effect on the nano-needle-like titanium oxide and a nano-needle-like nano-titanium surface, and a nano-porous titanium oxide sterilizing effect, and a nano-needle-like nano-titanium surface, and a nano-porous titanium oxide sterilizing effect, and a nano-porous titanium surface, and.
The preparation method of the antibacterial nano-porous material is characterized in that in the step one, the raw material for preparing the porous titanium is titanium powder or titanium fiber, and the raw material for preparing the porous titanium alloy is titanium alloy powder or titanium alloy fiber. The porous titanium or the porous titanium alloy with uniformly distributed pores is prepared by selecting the raw materials, and is favorable for forming a nano porous material with uniformly distributed nano pores.
The preparation method of the antibacterial nano-porous material is characterized in that the nano-porous material obtained in the third step consists of a porous titanium or porous titanium alloy matrix and a needle-shaped nano-porous titanium oxide surface layer. The porous base material has larger specific surface area, enhances the adhesive force of the surface layer on the base body, and avoids the cracking phenomenon of the surface layer.
Compared with the prior art, the invention has the following advantages:
1. The invention adopts electrodeposition and heat treatment in sequence to make Cu adhere and diffuse into porous titanium or porous titanium alloy to form multi-element alloy, then adopts nitric acid to carry out acid leaching treatment to remove copper in the multi-element alloy and form nano holes, and simultaneously carries out oxidation action, thereby forming a needle-shaped nano porous titanium oxide surface layer on the porous titanium or porous titanium alloy matrix to obtain the nano porous material with uniformly distributed nano pores.
2. The surface of the nano porous material prepared by the invention is provided with the needle-shaped nano porous titanium oxide which can pierce the surface of bacteria to realize the antibacterial and bactericidal functions, and meanwhile, in the process, the nano porous structure of the needle-shaped nano porous titanium oxide can generate capillary suction to the bacteria to actively sterilize, so that the antibacterial and bactericidal functions are further enhanced.
3. The nano porous material prepared by the invention can oxidize and decompose organic matters under the action of UV irradiation, thereby realizing the self-cleaning function in the antibacterial and bactericidal processes.
4. The preparation process has the advantages of simple flow, low production cost and low requirement on production equipment, and is suitable for large-scale industrial production.
The technical solution of the present invention is further described in detail by examples below.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, taking a porous titanium plate prepared from titanium powder as a cathode, graphite as an anode, and copper sulfate solution with the mass concentration of 25% as electrolyte, and performing electrodeposition to enable Cu 2+ in the electrolyte to be deposited on the surface of the porous titanium plate;
Secondly, placing the porous titanium plate with the surface deposited with Cu 2+ in the first step into an argon furnace for heat treatment, wherein the heat treatment temperature is 600 ℃, and the heat preservation time is 2 hours;
and step three, placing the porous titanium plate with the Cu 2+ deposited on the surface, which is subjected to the heat treatment in the step two, into a nitric acid solution with the mass concentration of 45%, and performing acid leaching treatment at the temperature of 70 ℃ to obtain a nano porous material, wherein the nano porous material consists of a porous titanium substrate and a needle-shaped nano porous titanium oxide surface layer.
through detection, the nano-porous material prepared by the embodiment has the bacteriostasis rate of more than 99% on escherichia coli and the bacteriostasis rate of more than 99% on staphylococcus aureus.
example 2
the embodiment comprises the following steps:
Step one, taking a porous titanium alloy plate prepared from titanium alloy fibers as a cathode, a platinum sheet as an anode, and a copper sulfate solution with the mass concentration of 25% as an electrolyte, and performing electrodeposition to deposit Cu 2+ in the electrolyte on the surface of the porous titanium plate;
secondly, placing the porous titanium alloy plate with the surface deposited with Cu 2+ in the first step into an argon furnace for heat treatment, wherein the heat treatment temperature is 600 ℃, and the heat preservation time is 2 hours;
And step three, placing the porous titanium alloy plate with the Cu 2+ deposited on the surface, which is subjected to the heat treatment in the step two, into a nitric acid solution with the mass concentration of 45%, and performing acid leaching treatment at the temperature of 70 ℃ to obtain a nano porous material, wherein the nano porous material consists of a porous titanium alloy matrix and a needle-shaped nano porous titanium oxide surface layer.
Through detection, the nano-porous material prepared by the embodiment has the bacteriostasis rate of more than 99% on escherichia coli and the bacteriostasis rate of more than 99% on staphylococcus aureus.
example 3
The embodiment comprises the following steps:
Step one, taking a porous titanium alloy plate prepared from titanium alloy powder as a cathode, taking graphite as an anode, taking a copper sulfate solution with the mass concentration of 20% as an electrolyte, and carrying out electrodeposition to enable Cu 2+ in the electrolyte to be deposited on the surface of the porous titanium plate;
Secondly, placing the porous titanium plate with the surface deposited with Cu 2+ in the first step into an argon furnace for heat treatment, wherein the heat treatment temperature is 500 ℃, and the heat preservation time is 2 hours;
And step three, placing the porous titanium plate with the Cu 2+ deposited on the surface, which is subjected to the heat treatment in the step two, into a nitric acid solution with the mass concentration of 40%, and performing acid leaching treatment at the temperature of 60 ℃ to obtain a nano porous material, wherein the nano porous material consists of a porous titanium alloy matrix and a needle-shaped nano porous titanium oxide surface layer.
Through detection, the nano-porous material prepared by the embodiment has the bacteriostasis rate of more than 99% on escherichia coli and the bacteriostasis rate of more than 99% on staphylococcus aureus.
Example 4
The embodiment comprises the following steps:
Step one, taking a porous titanium plate prepared from titanium fibers as a cathode, a platinum sheet as an anode, and a copper sulfate solution with the mass concentration of 10% as an electrolyte, and performing electrodeposition to deposit Cu 2+ in the electrolyte on the surface of the porous titanium plate;
secondly, placing the porous titanium plate with the surface deposited with Cu 2+ in the first step into an argon furnace for heat treatment, wherein the heat treatment temperature is 300 ℃, and the heat preservation time is 1 h;
And step three, placing the porous titanium plate with the Cu 2+ deposited on the surface, which is subjected to the heat treatment in the step two, into a nitric acid solution with the mass concentration of 30%, and performing acid leaching treatment at the temperature of 30 ℃ to obtain a nano porous material, wherein the nano porous material consists of a porous titanium substrate and a needle-shaped nano porous titanium oxide surface layer.
Through detection, the nano-porous material prepared by the embodiment has the bacteriostasis rate of more than 99% on escherichia coli and the bacteriostasis rate of more than 99% on staphylococcus aureus.
example 5
The embodiment comprises the following steps:
step one, taking a porous titanium plate prepared from titanium powder as a cathode, graphite as an anode, and a copper sulfate solution with the mass concentration of 30% as an electrolyte, and performing electrodeposition to deposit Cu 2+ in the electrolyte on the surface of the porous titanium plate;
secondly, placing the porous titanium plate with the surface deposited with Cu 2+ in the first step into an argon furnace for heat treatment, wherein the temperature of the heat treatment is 800 ℃, and the heat preservation time is 5 hours;
and step three, placing the porous titanium plate with the Cu 2+ deposited on the surface, which is subjected to the heat treatment in the step two, into a nitric acid solution with the mass concentration of 60%, and performing acid leaching treatment at the temperature of 70 ℃ to obtain a nano porous material, wherein the nano porous material consists of a porous titanium substrate and a needle-shaped nano porous titanium oxide surface layer.
through detection, the nano-porous material prepared by the embodiment has the bacteriostasis rate of more than 99% on escherichia coli and the bacteriostasis rate of more than 99% on staphylococcus aureus.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.

Claims (3)

1. A preparation method of an antibacterial nano-porous material is characterized by comprising the following steps:
Taking porous titanium or a porous titanium alloy as a cathode, graphite or a platinum sheet as an anode, and copper sulfate solution with the mass concentration of 10% -30% as electrolyte, and performing electrodeposition to enable Cu 2+ in the electrolyte to be deposited on the surface of the porous titanium or the porous titanium alloy;
Secondly, placing the porous titanium or the porous titanium alloy with the surface deposited with Cu 2+ in the step one into an argon furnace for heat treatment, wherein the temperature of the heat treatment is 300-800 ℃, and the heat preservation time is 1-5 h;
and step three, placing the porous titanium or the porous titanium alloy with the Cu 2+ deposited on the surface, which is subjected to the heat treatment in the step two, into a nitric acid solution for acid leaching treatment to obtain the nano porous material, wherein the mass concentration of the nitric acid solution is 30-60%, and the temperature of the acid leaching treatment is 30-70 ℃.
2. The method for preparing an antibacterial nano-porous material according to claim 1, wherein the raw material for preparing the porous titanium in the step one is titanium powder or titanium fiber, and the raw material for preparing the porous titanium alloy is titanium alloy powder or titanium alloy fiber.
3. The method for preparing antibacterial nano-porous material according to claim 1, wherein the nano-porous material obtained in the third step consists of a porous titanium or porous titanium alloy matrix and a needle-shaped nano-porous titanium oxide surface layer.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111560635A (en) * 2020-06-18 2020-08-21 暨南大学 Titanium alloy with antibacterial nano-porous copper-zinc coating, and preparation method and application thereof

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CN106560521A (en) * 2016-10-30 2017-04-12 宝鸡文理学院 Medical porous titanium and titanium alloy preparation method

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Publication number Priority date Publication date Assignee Title
JP2006089297A (en) * 2004-09-21 2006-04-06 Shiseido Co Ltd Aegagropila-shaped porous titanium oxide having high photocatalytic activity
CN106560521A (en) * 2016-10-30 2017-04-12 宝鸡文理学院 Medical porous titanium and titanium alloy preparation method

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李萍: "微纳米多孔a-钛的制备与组织结构及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111560635A (en) * 2020-06-18 2020-08-21 暨南大学 Titanium alloy with antibacterial nano-porous copper-zinc coating, and preparation method and application thereof
CN111560635B (en) * 2020-06-18 2021-07-27 暨南大学 Titanium alloy with antibacterial nano-porous copper-zinc coating, and preparation method and application thereof

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